US4148771A - Method of making novel rubbery block copolymers and pressure-sensitive adhesives - Google Patents

Method of making novel rubbery block copolymers and pressure-sensitive adhesives Download PDF

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Publication number
US4148771A
US4148771A US05/809,491 US80949177A US4148771A US 4148771 A US4148771 A US 4148771A US 80949177 A US80949177 A US 80949177A US 4148771 A US4148771 A US 4148771A
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United States
Prior art keywords
adhesive composition
composition according
monovinyl
substituted aromatic
aromatic hydrocarbon
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Expired - Lifetime
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US05/809,491
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English (en)
Inventor
Larry L. Nash
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Phillips Petroleum Co
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Phillips Petroleum Co
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Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to US05/809,491 priority Critical patent/US4148771A/en
Priority to AU35715/78A priority patent/AU502743B1/en
Priority to JP6215078A priority patent/JPS5410396A/ja
Priority to FR7818303A priority patent/FR2395283A1/fr
Priority to ES470980A priority patent/ES470980A1/es
Priority to DE19782827284 priority patent/DE2827284A1/de
Priority to CA306,013A priority patent/CA1108794A/fr
Priority to IT24872/78A priority patent/IT1096792B/it
Priority to IT7824942A priority patent/IT7824942A0/it
Priority to BE188800A priority patent/BE868401A/fr
Application granted granted Critical
Publication of US4148771A publication Critical patent/US4148771A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/901—Radial block

Definitions

  • This invention relates in one aspect to a new method of making conjugated diene/monovinyl-substituted aromatic hydrocarbon teleblock copolymers (either linear or radial). In another aspect it relates to the new copolymers which result. In still another aspect, this invention relates to improved pressure-sensitive adhesives.
  • novel rubbery teleblock copolymers of this invention are represented by the general formula
  • S represents a block of polymerized monovinyl-substituted aromatic hydrocarbon molecules
  • D represents a block of polymerized conjugated diene molecules
  • Y represents the residue of a polyfunctional coupling agent
  • x is an integer of at least 2 and can be (ideally) equal to the number of reactive sites on the polyfunctional coupling agent
  • novel copolymers can be either linear or radial although the radial (or branched) copolymers are preferred because of their superior properties in adhesives.
  • the preparation of branched copolymers from monolithium-terminated polymers by coupling with agents having at least three reactive sites is broadly disclosed in Zelinski, et al, U.S. Pat. No. 3,281,383; and that patent is hereby incorporated by reference.
  • the conjugated dienes useful with the monovinyl-substituted aromatic hydrocarbon in preparation of the novel teleblock copolymers are those having 4 to 8 carbon atoms.
  • Examples of these C 4 -C 8 conjugated dienes are: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, 2,4-hexadiene, 1,3-octadiene, and the like.
  • Especially preferred are butadiene and isoprene.
  • the monovinyl-substituted aromatic hydrocarbons which can be used in the preparation of the novel copolymer have 8-12 carbon atoms per molecule.
  • Examples are styrene, 3-methylstyrene, 4-n-propylstyrene, 4-t-butylstyrene and the like. Especially preferred is styrene.
  • novel teleblock copolymers will generally contain conjugated diene and monovinyl-substituted aromatic hydrocarbon in amounts within the range of about 90:10 to about 60:40 parts by weight of conjugated diene:monovinyl-substituted aromatic hydrocarbon. About 85:15 to about 70:30 parts by weight of conjugated diene:monovinyl-substituted aromatic hydrocarbon is the especially preferred range for best adhesive properties.
  • any organomonolithium initiator known in the art can be used to initiate polymerization of the conjugated diene and monovinyl-substituted aromatic hydrocarbon to produce the teleblock copolymers in this invention.
  • Those hydrocarbyllithium compounds containing from 1 to about 20 carbon atoms are generally useful.
  • examples of such initiators include methyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, n-eicosyllithium, phenyllithium, p-tolyllithium, cyclohexyllithium and the like.
  • the n-alkyllithium compounds give polymers which result in adhesives with especially good creep resistance, and n-butyllithium is the especially preferred initiator.
  • the amount of initiator used will be varied, depending upon the desired molecular weight of the resultant copolymer.
  • the teleblock copolymers of this invention can vary from relatively low molecular weight rubbers up to those having a molecular weight of 500,000 or more.
  • the initiator levels useful in preparing the inventive copolymers for the inventive adhesives are generally in the range of about 0.25 to about 40 gram millimoles per 100 grams of total monomers.
  • a polar compound such as acyclic or cyclic ethers or tertiary amines
  • a polar compound is preferably employed in the polymerization of the conjugated diene and monovinyl-substituted aromatic hydrocarbon in order to increase the rate of polymerization.
  • the reaction will proceed without the polar compound not only at a very slow rate. If a sec- or tert-alkyllithium initiator were used, the reaction rate would be faster; but a polar compound would still be preferred.
  • Diethyl ether, tetrahydrofuran and tetramethylethylenediamine are among those frequently used in amounts ranging from about 0.01 to about 100 and usually from about 0.2 to about 10 gram millimoles per 100 grams of monomer.
  • hydrocarbon diluent Use of a hydrocarbon diluent is much to be preferred in the polymerization process for ease in mixing and for temperature control.
  • Common diluents which are well known in the art to be useful in solution polymerization processes include n-hexane, n-heptane, cyclohexane, benzene, toluene, and the like and mixtures thereof.
  • a reasonable range of amount of diluent that can be used is about 50-2000 parts by weight per 100 parts by weight of monomer.
  • the polymerization process of this invention involves the incremental addition of both organomonolithium initiator and monovinyl-substituted aromatic hydrocarbon.
  • a portion of the total monovinyl-substituted aromatic hydrocarbon monomer and a portion of the organolithium initiator are mixed with the diluent in the reactor.
  • the remainder of monovinyl-substituted aromatic hydrocarbon and initiator is added to the reactor in at least one more increment and in as many increments as desired. This incremental addition of both initiator and first monomer provides much greater control over the reaction than could be obtained by incremental addition of only the initiator.
  • the polymerization process is generally carried out at temperatures in the range of about -25° to about 150° C., preferably about 25° to about 125° C. It is especially convenient to employ a process in which essentially adiabatic conditions are maintained; i.e., the heat liberated by the polymerization reaction is not removed by use of internal or external cooling devices, but the temperature of the polymerization system is allowed to rise until the polymerization reaction is essentially complete and the temperature of the system then decreases.
  • reaction system can be maintained under positive pressure, which pressure can be applied either by the addition of an inert gas, such as nitrogen, or by only the vapor pressures of the components of the reaction system.
  • Convenient pressures can be in the range of about 50 to about 10,000 kPa and preferably and more conveniently in the range of about 50 to about 800 kPa.
  • Polymerization times will generally be determined by the temperature, as well as by the reactivities of the components. Normal polymerization times will generally be in the range of about 0.1 min to about 24 hours and preferably about 1 minute to about one hour.
  • a polyfunctional coupling agent (containing at least two reactive sites) is added to the unquenched reaction mixture to produce the coupled copolymer.
  • This agent must be added before any material such as water, acid or alcohol is added.
  • the temperature of the coupling reaction can vary over a wide range and is conveniently the same as that used for polymerization. At normal polymerization temperatures, i.e., above about 25° C., the coupling reaction occurs rapidly, i.e., in the range of several seconds to about 1 hour.
  • the polyfunctional coupling agents which are added to the polymerization mixture after completion of the polymerization reaction include those polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides and the like which are described fully in U.S. Pat. No. 3,281,383.
  • the polyhalides, especially the silicon tetrahalides, such as silicon tetrachloride, are the preferred coupling agents.
  • the optimum amount of polyfunctional coupling agent to be employed will be that amount of coupling agent which contains one gram-equivalent of coupling agent for each gram-equivalent of lithium-terminated polymer molecules.
  • each reactive functional site in the coupling agent will react with one carbon-lithium bond in the living polymer. Any given agent may demonstrate an effective functionality which is less than theoretical, but it is the actual reacting sites which are considered in determining functionality.
  • the resulting final product is either a linear polymer when using a difunctional agent or a radial polymer (in which three or more polymer chains extend radially from the centralized coupling agent residue) when using an agent having 3 or more functional groups. It may sometimes be desirable to employ a slight excess of coupling agent such as up to 25 mole percent in excess of the stoichiometric amount of coupling agent.
  • a currently convenient process for preparing the teleblock copolymers of the invention is as follows. Care must be taken to exclude moisture or oxygen from the polymerization system. A portion of the monovinyl-substituted aromatic hydrocarbon and the diluent in a suitable reactor are maintained at the desired temperature for initiation of polymerization. Introduction of a portion of the organomonolithium compound initiates the polymerization of the monovinyl-substituted aromatic hydrocarbon monomer. At least one more portion of both the monovinyl-substituted aromatic hydrocarbon and initiator are added to the reaction vessel, and polymerization is allowed to proceed.
  • conjugated diene monomer is introduced into the unquenched polymerization system.
  • the bifunctional or polyfunctional coupling agent is added.
  • the coupling reaction is complete, if any carbon-lithium remains it can be inactivated by addition of water, alcohol or acid.
  • the resultant teleblock copolymer is then isolated by any suitable means well known in the art, such as coagulation by alochol or steam-stripping of volatiles, followed by appropriate drying procedures.
  • the range of heterogeneity index of the monovinyl-substituted aromatic hydrocarbon portion of the copolymer which would be within the scope of the invention is about 1.4 to about 3.0; and the preferred range is about 1.4 to about 2.0.
  • the heterogeneity index of the total copolymer in this invention will generally lie within the range of about 1.1 to about 1.4; and this range is defined to be "regular”.
  • the heterogeneity index of the monovinyl-substituted aromatic hydrocarbon portion of the copolymer is substantially larger than the heterogeneity index of the total copolymer, substantially larger being defined in this invention as at least about 0.1 units larger.
  • reaction mixture of the first increment of monovinyl-substituted aromatic compound, polar compound, and hydrocarbon diluent (if present) it is desirable to allow the reaction mixture of the first increment of monovinyl-substituted aromatic compound, polar compound, and hydrocarbon diluent (if present) to reach the optimal polymerization temperature before the first increment of initiator is added. Also, for control of the reaction, it is desirable that the second and other remaining increments of initiator be put into the reactor either prior to or simultaneous with the second or other remaining increments of monovinyl-substituted aromatic hydrocarbon.
  • inventive adhesive formulations of this invention include, in addition to the teleblock copolymers, a tackifier or tackifiers. Plasticizers, stabilizers, and diluent may be included, if desired.
  • Suitable tackifiers include any of the resinous substances known in the art for enhancing tack of adhesive compositions.
  • useful tackifiers include rosin, rosin derivatives, polyterpene resins, phenolic resins, coumarone-indene resins and the like.
  • plasticizers well known in the adhesives art can be employed in the inventive formulations.
  • plasticizers include the well known extender oils, aromatic, paraffinic or naphthenic, as well as a wide variety of liquid polymers.
  • Stabilizers are generally employed in the inventive adhesive formulations to inhibit degradation of the adhesive by exposure to heat, light, oxygen, ozone, etc.
  • Examples of common stabilizers which are useful in the inventive formulations include the well-known hindered phenols, phosphites, phenolic phosphites, thiodicarboxylate esters and the like, as well as mixtures thereof.
  • the adhesives of this invention can be applied to substrates as solutions, emulsions, dispersions or hot-melts.
  • the formulations can contain hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene, etc.
  • suitable carriers such as water and suitable emulsifiers are present in the formulations.
  • the adhesive formulations will preferably contain the various ingredients in amounts given in the following recipe.
  • Runs 2 and 3 were carried out according to this invention to prepare 80/20 butadiene/styrene radial teleblock copolymers employing incremental addition of both styrene and n-butyllithium.
  • the polymers made in Runs 1, 2 and 3 were employed in hot melt pressure sensitive adhesives.
  • the adhesives were formulated according to the following recipe. Evaluations of the adhesives are recorded in Table III and are labeled Runs 4, 5 and 6.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)
US05/809,491 1977-06-23 1977-06-23 Method of making novel rubbery block copolymers and pressure-sensitive adhesives Expired - Lifetime US4148771A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US05/809,491 US4148771A (en) 1977-06-23 1977-06-23 Method of making novel rubbery block copolymers and pressure-sensitive adhesives
AU35715/78A AU502743B1 (en) 1977-06-23 1978-05-03 Rubbery block copolymers
JP6215078A JPS5410396A (en) 1977-06-23 1978-05-24 Rubbery block copolymer* preparation and adhesive composition thereof
FR7818303A FR2395283A1 (fr) 1977-06-23 1978-06-19 Procede de fabrication de copolymeres sequences caoutchouteux et adhesifs sensibles a la pression, prepares a partir de ces copolymeres
ES470980A ES470980A1 (es) 1977-06-23 1978-06-21 Procedimiento para la obtencion de copolimeros cauchotosos acoplados de hidrocarburos aromaticos monovinil sustituidosndieno conjugado
DE19782827284 DE2827284A1 (de) 1977-06-23 1978-06-21 Blockpolymere mit vom gesamtmolekuel unterschiedlichem heterogenitaetsindex und verfahren zu deren herstellung
CA306,013A CA1108794A (fr) 1977-06-23 1978-06-22 Procede d'obtention de nouveaux copolymeres sequences, caoutchoutes et d'adhesifs par pression
IT24872/78A IT1096792B (it) 1977-06-23 1978-06-22 Metodo per la preparazione di copolimeri a blocchi a carattere di gomma e adesivi sensibili alla pressione
IT7824942A IT7824942A0 (it) 1977-06-23 1978-06-23 Metodo per la preparazione di copolimeri a blocchi a carattere di gomma elastica e adesivi sensibili alla pressione.
BE188800A BE868401A (fr) 1977-06-23 1978-06-23 Procede de fabrication de copolymeres sequences, caoutchouteux et adhesifs sensibles a la pression, prepares a partir de ces copolymeres

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US05/809,491 US4148771A (en) 1977-06-23 1977-06-23 Method of making novel rubbery block copolymers and pressure-sensitive adhesives

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JP (1) JPS5410396A (fr)
AU (1) AU502743B1 (fr)
BE (1) BE868401A (fr)
CA (1) CA1108794A (fr)
DE (1) DE2827284A1 (fr)
ES (1) ES470980A1 (fr)
FR (1) FR2395283A1 (fr)
IT (2) IT1096792B (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4244855A (en) * 1978-09-26 1981-01-13 Abbott Laboratories Liquid golf ball center
US4256853A (en) * 1979-09-11 1981-03-17 Phillips Petroleum Company Nonlaminating polyphenylene ether blends
US4409369A (en) * 1980-03-03 1983-10-11 The Dow Chemical Company Transparent impact resin and process for the preparation thereof
JPS58213010A (ja) * 1982-06-07 1983-12-10 Japan Synthetic Rubber Co Ltd 分岐状ブロック共重合体
US4464504A (en) * 1982-02-22 1984-08-07 Muanyagipari Kutato Intezet and Hutogepgyar Freon-corrosion, impact and cold resistant flame-retardant polystyrene blend containing zeolites having cation(s) of Mg, Co, Sb, or Mo
US4554324A (en) * 1982-09-16 1985-11-19 Minnesota Mining And Manufacturing Co. Acrylate copolymer pressure-sensitive adhesive composition and sheet materials coated therewith
US4780367A (en) * 1983-06-27 1988-10-25 Minnesota Mining And Manufacturing Company Tackified star block copolymer pressure-sensitive adhesive composition and the sheet materials coated therewith
US4914248A (en) * 1986-03-13 1990-04-03 Asahi Kasei Kogyo Kabushiki Kaisha Diene polymers, process for production, thereof, and rubber compositions containing same
US5057366A (en) * 1982-09-16 1991-10-15 Minnesota Mining And Manufacturing Company Acrylate copolymer pressure-sensitive adhesive coated sheet material
US5118762A (en) * 1990-04-11 1992-06-02 Shell Oil Company Styrene-isoprene-styrene block copolymer composition for low viscosity low temperature hot melt adhesives
US5296547A (en) * 1993-01-28 1994-03-22 Minnesota Mining And Manufacturing Company Block copolymer having mixed molecular weight endblocks
US5399627A (en) * 1989-08-11 1995-03-21 The Dow Chemical Company Radial styrene-isoprene-butadiene multi-armed block copolymers and compositions and articles containing block copolymers
US6288159B1 (en) 1996-08-12 2001-09-11 Tactyl Technologies, Inc. S-EB-S block copolymer/oil aqueous dispersion and its use in forming articles
US6630531B1 (en) 2000-02-02 2003-10-07 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US20030211308A1 (en) * 2001-02-02 2003-11-13 Khandpur Ashish K Adhesive for bonding to low surface energy surfaces

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5158781A (en) * 1974-11-19 1976-05-22 Tahara Shoei Kiko Kk Kyokuzahyokei niokeru naraiseigyohoshiki
JPS5169284A (en) * 1974-11-19 1976-06-15 Tahara Shoei Kiko Kk Jidonaraikensakuseigyosochi
JPS58141269A (ja) * 1982-02-16 1983-08-22 Asahi Chem Ind Co Ltd 熱溶融型粘着剤組成物
US5037411A (en) * 1988-11-09 1991-08-06 H. B. Fuller Company Disposable article multi-line construction adhesive
JP2553766Y2 (ja) * 1988-12-29 1997-11-12 旭電化工業株式会社 自動車内配線のシール構造

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US3281383A (en) * 1962-08-09 1966-10-25 Phillips Petroleum Co Branched polymers prepared from monolithium-terminated polymers and compounds having at least three reactive sites
US3637554A (en) * 1966-11-07 1972-01-25 Phillips Petroleum Co Polystyrene compositions
US3639517A (en) * 1969-09-22 1972-02-01 Phillips Petroleum Co Resinous branched block copolymers
US3658740A (en) * 1969-12-05 1972-04-25 Phillips Petroleum Co Pressure sensitive adhesives
US3753936A (en) * 1970-02-18 1973-08-21 Phillips Petroleum Co Branched rubbery block copolymer adhesive
US3950291A (en) * 1974-06-03 1976-04-13 Phillips Petroleum Company Hot-melt adhesive composition
CA997889A (en) 1970-05-22 1976-09-28 Shell Internationale Research Maatschappij, N.V. Unsymmetrical branched non-linear block copolymers
US3993613A (en) * 1975-02-24 1976-11-23 Phillips Petroleum Company Adhesive composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984369A (en) * 1975-05-15 1976-10-05 Shell Oil Company Sealant

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281383A (en) * 1962-08-09 1966-10-25 Phillips Petroleum Co Branched polymers prepared from monolithium-terminated polymers and compounds having at least three reactive sites
US3637554A (en) * 1966-11-07 1972-01-25 Phillips Petroleum Co Polystyrene compositions
US3639517A (en) * 1969-09-22 1972-02-01 Phillips Petroleum Co Resinous branched block copolymers
US3658740A (en) * 1969-12-05 1972-04-25 Phillips Petroleum Co Pressure sensitive adhesives
US3753936A (en) * 1970-02-18 1973-08-21 Phillips Petroleum Co Branched rubbery block copolymer adhesive
CA997889A (en) 1970-05-22 1976-09-28 Shell Internationale Research Maatschappij, N.V. Unsymmetrical branched non-linear block copolymers
US3950291A (en) * 1974-06-03 1976-04-13 Phillips Petroleum Company Hot-melt adhesive composition
US3993613A (en) * 1975-02-24 1976-11-23 Phillips Petroleum Company Adhesive composition

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4244855A (en) * 1978-09-26 1981-01-13 Abbott Laboratories Liquid golf ball center
US4256853A (en) * 1979-09-11 1981-03-17 Phillips Petroleum Company Nonlaminating polyphenylene ether blends
US4409369A (en) * 1980-03-03 1983-10-11 The Dow Chemical Company Transparent impact resin and process for the preparation thereof
US4464504A (en) * 1982-02-22 1984-08-07 Muanyagipari Kutato Intezet and Hutogepgyar Freon-corrosion, impact and cold resistant flame-retardant polystyrene blend containing zeolites having cation(s) of Mg, Co, Sb, or Mo
JPS58213010A (ja) * 1982-06-07 1983-12-10 Japan Synthetic Rubber Co Ltd 分岐状ブロック共重合体
US4554324A (en) * 1982-09-16 1985-11-19 Minnesota Mining And Manufacturing Co. Acrylate copolymer pressure-sensitive adhesive composition and sheet materials coated therewith
US5057366A (en) * 1982-09-16 1991-10-15 Minnesota Mining And Manufacturing Company Acrylate copolymer pressure-sensitive adhesive coated sheet material
US4780367A (en) * 1983-06-27 1988-10-25 Minnesota Mining And Manufacturing Company Tackified star block copolymer pressure-sensitive adhesive composition and the sheet materials coated therewith
US4914248A (en) * 1986-03-13 1990-04-03 Asahi Kasei Kogyo Kabushiki Kaisha Diene polymers, process for production, thereof, and rubber compositions containing same
US5399627A (en) * 1989-08-11 1995-03-21 The Dow Chemical Company Radial styrene-isoprene-butadiene multi-armed block copolymers and compositions and articles containing block copolymers
US5118762A (en) * 1990-04-11 1992-06-02 Shell Oil Company Styrene-isoprene-styrene block copolymer composition for low viscosity low temperature hot melt adhesives
US5296547A (en) * 1993-01-28 1994-03-22 Minnesota Mining And Manufacturing Company Block copolymer having mixed molecular weight endblocks
US5393787A (en) * 1993-01-28 1995-02-28 Minnesota Mining And Manufacturing Company Block copolymer having mixed molecular weight endblocks
US6288159B1 (en) 1996-08-12 2001-09-11 Tactyl Technologies, Inc. S-EB-S block copolymer/oil aqueous dispersion and its use in forming articles
US6414083B2 (en) 1996-08-12 2002-07-02 Tactyl Technologies, Inc. S-EB-S block copolymer/oil aqueous dispersion and its use in forming articles
US6630531B1 (en) 2000-02-02 2003-10-07 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US20040082700A1 (en) * 2000-02-02 2004-04-29 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US20040229000A1 (en) * 2000-02-02 2004-11-18 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US7163741B2 (en) 2000-02-02 2007-01-16 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US7491434B2 (en) 2000-02-02 2009-02-17 3M Innovative Properties Company Adhesive for bonding to low surface energy surfaces
US20030211308A1 (en) * 2001-02-02 2003-11-13 Khandpur Ashish K Adhesive for bonding to low surface energy surfaces

Also Published As

Publication number Publication date
IT7824872A0 (it) 1978-06-22
AU502743B1 (en) 1979-08-09
JPS5410396A (en) 1979-01-25
ES470980A1 (es) 1979-02-01
IT1096792B (it) 1985-08-26
BE868401A (fr) 1978-12-27
IT7824942A0 (it) 1978-06-23
JPS5541686B2 (fr) 1980-10-25
CA1108794A (fr) 1981-09-08
FR2395283B1 (fr) 1980-11-28
DE2827284A1 (de) 1979-04-05
FR2395283A1 (fr) 1979-01-19

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